CN104891559B - With titanium dioxide for titanium source synthesis Li doping PbTiO3the method of nano-particle and product and application - Google Patents
With titanium dioxide for titanium source synthesis Li doping PbTiO3the method of nano-particle and product and application Download PDFInfo
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Abstract
The invention discloses a kind of with titanium dioxide for titanium source synthesis Li doping PbTiO3The method of nano-particle, after being mixed with deionized water by KOH, adds TiO2, after stirring, it is sequentially added into Pb (NO3)2And LiNO3, obtain precursor pulp after stirring, hydro-thermal reaction 12～16h at 200～220 DEG C, obtain described Li doping PbTiO3Nano-particle；In described precursor pulp, the molar concentration of KOH is 4～6mol/L, Li+Molar concentration is 0.1～0.2mol/L, and titanium lead ratio is 1:1～1:1.1.The invention discloses a kind of synthesis Li doping PbTiO3The method of nano-particle, with titanium dioxide for titanium source, by the accuracy controlling to technological parameter, has prepared Li doping PbTiO3Nano-particle, technical process is simple, it is easy to control, pollution-free, low cost, it is simple to amplifies and produces.
Description
Technical field
The present invention relates to the technical field of Inorganic Non-metallic Materials, particularly relate to a kind of with titanium dioxide for titanium source synthesis Li doping PbTiO3Method of nano-particle and products thereof and application.
Background technology
Perovskite composite oxide is to have perovskite CaTiO3The big compounds of the one of structure.Owing to it has the electric property of excellence, piezoelectric property, superconductivity, perovskite composite oxide has wide research and application prospect at aspects such as gas sensitive, ferroelectric material, purifying vehicle exhaust, organic synthesis catalysis.
PbTiO3It it is one of a kind of typical perovskite composite oxide, it has ferroelectricity, piezoelectricity, high Curie temperature, low-k and significant anisotropy, it is to prepare pyroelectricity, infrared air-sensitive and the quality material of piezoelectric ceramics, at microelectronics, photoelectric field, high frequency filter, the field such as infrared thermal release electric detector and piezo ultrasound transducers has a wide range of applications.
At present, PbTiO3Preparation method a lot, as sol-gel process, coprecipitation, oxidesintering method, microemulsion method, acetate method, hydro-thermal method obtain.Research shows, uses hydrothermal synthesis method, can prepare that particle diameter is tiny, degree of crystallinity is high at a lower temperature, reunites less, the nanometer split of sintering activity height, compound with regular structure, good dispersion.
As the Chinese patent literature of Publication No. CN104018226A discloses the cubic Perovskite Phase PbTiO of a kind of nano-particles self assemble3The preparation method of micron film, use hydro-thermal method, with titanium dioxide, potassium hydroxide, plumbi nitras, deionized water and dehydrated alcohol as reaction mass, at 120～200 DEG C, in reactor, carry out hydro-thermal reaction, obtain by the cubic Perovskite Phase PbTiO of nano-particles self assemble3Micron film.
Research about nano material in recent years proves, the performance of nano-powder material is not only affected by its nano-scale, and its granule-morphology the most also plays conclusive impact.Ca-Ti ore type PbTiO3Pattern the same with size, the performance of material can be had a strong impact on.
Summary of the invention
The invention discloses a kind of synthesis Li doping PbTiO3The method of nano-particle, with titanium dioxide for titanium source, by the accuracy controlling to technological parameter, has prepared Li doping PbTiO3Nano-particle, technical process is simple, it is easy to control, pollution-free, low cost, it is simple to amplifies and produces.
A kind of with titanium dioxide for titanium source synthesis Li doping PbTiO3The method of nano-particle, comprises the steps:
After being mixed with deionized water by KOH, add TiO2, after stirring, it is sequentially added into Pb (NO3)2And LiNO3, obtain precursor pulp after stirring, hydro-thermal reaction 12～16h at 200～220 DEG C, obtain described Li doping PbTiO3Nano-particle；
In described precursor pulp, the molar concentration of KOH is 4～6mol/L, Li+Molar concentration is 0.1～0.2mol/L, and titanium lead ratio is 1:1～1.1.
The present invention is using titanium dioxide as titanium source presoma, with Pb (NO3)2For lead source, KOH is mineralizer, and introduces different amounts of LiNO in reaction mass3The PbTiO of synthesis Li doping3Nano-particle.
As preferably, described hydro-thermal reaction is carried out in reactor, and in reactor, compactedness is 60～80%.When compactedness deficiency, can be adjusted by adding deionized water, but must ensure that in the precursor pulp after regulation, the molar concentration of KOH is 4～6mol/L, Li+Molar concentration is 0.1～0.2mol/L, and titanium lead ratio is 1:1～1.1.
As preferably, described hydrothermal reaction condition is: react 12～16h at 200～220 DEG C..
As preferably, the crude product of hydro-thermal reaction is after deionized water and dehydrated alcohol clean successively, then drying obtains end product.
Raw material plumbi nitras used by the present invention, the purity of mineralizer potassium hydroxide, solvent dehydrated alcohol and deionized water is all not less than chemical pure.
The invention discloses the Li doping PbTiO prepared according to described method3Nano-particle, the metal Li ion of doping mainly instead of PbTiO3Pb in lattice, forms displaced type doping, and owing to Li ionic radius is less than Pb ionic radius, lattice paprmeter diminishes, therefore along with LiNO in preparation process3Consumption increase, the skew of the diffraction maximum phase wide-angle of XRD.It is likely to a small amount of Li simultaneously and occupy gap digit, form gap shape doping.Due to the doping of Li, result in O room and Ti trivalent particle defects so that lithium doping PbTiO3There is excellent visible light catalytic performance, especially splendid to the Photocatalytic Degradation Property of methylene blue.
Compared with prior art, present invention have the advantage that
The present invention, by the accuracy controlling to technological parameter, has prepared Li doping PbTiO3Nano-particle, technical process is simple, it is easy to control, pollution-free, low cost, it is simple to amplifies and produces.
Accompanying drawing explanation
The Li that Fig. 1 is embodiment 1 and embodiment 2 is prepared respectively adulterates PbTiO3The XRD figure spectrum of nano-particle, and provide the PbTiO of preparation in comparative example 13The XRD figure of nano-particle is composed as a comparison；
A () is comparative example 1, (b) is embodiment 1, and (c) is embodiment 2；
The Li that Fig. 2 is embodiment 1 and embodiment 2 is prepared respectively adulterates PbTiO3The XRD partial enlargement collection of illustrative plates of nano-particle, and provide the PbTiO of preparation in comparative example 13The XRD figure of nano-particle is composed as a comparison；
A () is comparative example 1, (b) is embodiment 1, and (c) is embodiment 2；
The Li that Fig. 3 is embodiment 1 and embodiment 2 is prepared respectively adulterates PbTiO3The XPS collection of illustrative plates of the Ti of nano-particle, and provide the PbTiO of preparation in comparative example 13The XPS collection of illustrative plates of the Ti of nano-particle is as a comparison；
A () is comparative example 1, (b) is embodiment 1, and (c) is embodiment 2；
Fig. 4 is the Li doping PbTiO that embodiment 1,2 is prepared respectively3The stereoscan photograph of nano-particle, and provide the PbTiO of preparation in comparative example 13The stereoscan photograph of nano-particle is as a comparison；
A () is comparative example 1, (b) is embodiment 1, and (c) is embodiment 2；
Fig. 5 is the Li doping PbTiO of embodiment 1 preparation3The efficiency chart of the photocatalytic degradation methylene blue of nano-particle；
Fig. 6 is the Li doping PbTiO of embodiment 2 preparation3The efficiency chart of the photocatalytic degradation methylene blue of nano-particle；
Fig. 7 is the PbTiO of comparative example 1 preparation3The efficiency chart of the photocatalytic degradation methylene blue of nano-particle.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
1) 4.5g KOH is dissolved in 20ml deionized water is configured to the KOH aqueous solution of 4M, be slowly added 6mmolTi0 the most inward2, stir 0.5h；
2) to step 1) gained solution is initially charged 6mmol Pb (NO3)2, add LiNO3And deionized water, obtain precursor pulp after stirring, move into the reactor of 50mL, airtight, it is placed in 200 DEG C of insulations 12h, Hydrothermal Synthesis Li+The PbTiO of adulterated with Ca and Ti ore structure3Nano-particle.
In described precursor pulp, LiNO3Concentration is 0.1mol/L.Obtain product respectively with 1% dilute HNO3Clean with deionized water, at 60 DEG C, be dried 24h.
Embodiment 2:
1) 6.7g KOH is dissolved in 20ml deionized water is configured to the KOH aqueous solution of 6M, be slowly added 6mmolTi0 the most inward2, stir 0.5h；
2) to step 1) gained solution is initially charged 6mmol Pb (NO3)2, add LiNO3And deionized water, obtain precursor pulp after stirring, move into the reactor of 50mL, airtight, it is placed in 200 DEG C of insulations 12h, Hydrothermal Synthesis Li+Adulterated with Ca and Ti ore structure PbTiO3Nano-particle.
In described precursor pulp, LiNO3Concentration is 0.2mol/L.Obtain product respectively with 1% dilute HNO3Clean with deionized water, at 60 DEG C, be dried 24h.
Comparative example 1
1) 6.7g KOH is dissolved in 20ml deionized water is configured to the KOH aqueous solution of 6M, be slowly added 6mmol Ti0 the most inward2, stir 0.5h；
2) to step 1) gained solution is initially charged 6mmol Pb (NO3)2, add deionized water, after stirring, obtain precursor pulp, move into the reactor of 50mL, airtight, it is placed in 200 DEG C of insulations 12h, the PbTiO of Hydrothermal Synthesis perovskite structure3Nano-particle.
Obtain product respectively with 1% dilute HNO3Clean with deionized water, at 60 DEG C, be dried 24h.
X-ray diffraction (XRD) collection of illustrative plates of the product that embodiment 1,2 and comparative example 1 are prepared respectively is shown in Fig. 1 and Fig. 2, and from two figures, Li adulterates PbTiO3The diffraction maximum curve of nano-particle and pure PbTiO3Diffraction maximum curve is sufficiently close to, owing to doping causes distortion of lattice, and the phenomenon that the most oriented right avertence of diffraction maximum is moved.
The XPS collection of illustrative plates of the Ti of the product that embodiment 1,2 and comparative example 1 are prepared respectively is shown in Fig. 3, can substantially observe and pure PbTiO3In be positioned at the Ti at 458.3eV4+In conjunction with comparing, the PbTiO that Li mixes3Middle Ti 2p combines can certain displacement, and peak position is asymmetric, and this is due to part Ti4+Ion appraises at the current rate as Ti3+Caused.
The SEM photograph of the product that embodiment 1,2 and comparative example 1 are prepared respectively is shown in Fig. 4, as seen from the figure, when being not added with LiNO3Time, product is made up of, along with LiNO a large amount of polygon ball nano-particle3The increase of addition, is then mainly small size fluidized agglomerate of nano-size particles in product, the size of nano-particle is about 5～about 20nm.
Comparative example 2
Use preparation technology same as in Example 1, differ only in, step 2) in, in described precursor pulp, KOH concentration is 8mol/L, LiNO3Concentration is 0.8mol/L.
Experimental product is LiTiO2Nano-particle.The doping of Li is limited, as the LiNO introduced3Amount exceed a certain amount of after, PbTiO will be suppressed3Formation, obtain LiTiO2Nano-particle.
Application examples
The Li doping PbTiO that embodiment 1,2 is prepared respectively3PbTiO prepared by nano-particle and comparative example3Nano-particle mixes for 1:50 in mass ratio with methylene blue (MB), measures the uv-visible absorption spectra of three (λ 400nm) photocatalytic degradation MB under visible light illumination, characterizes its catalytic performance.
Comparison diagram 5,6 understands with Fig. 7, and Li doping can improve PbTiO to a certain extent3The photocatalysis performance of nano-particle, and along with the increase of Li doping content, catalytic performance gradually promotes, and when the doping of Li is 0.2mol/L, MB basic degraded in 60min is complete.
Claims (2)
1. one kind with titanium dioxide for titanium source synthesis Li adulterate PbTiO3The method of nano-particle, its
It is characterised by, comprises the steps:
1) 4.5g KOH is dissolved in 20ml deionized water is configured to the KOH aqueous solution of 4M, limit
Stirring limit is slowly added 6mmolTi0 inward2, stir 0.5h；
2) to step 1) gained solution is initially charged 6mmol Pb (NO3)2, add LiNO3With
Deionized water, obtains precursor pulp after stirring, move into the reactor of 50mL, airtight,
It is placed in 200 DEG C of insulations 12h, Hydrothermal Synthesis Li+The PbTiO of adulterated with Ca and Ti ore structure3Nano-particle；
In described precursor pulp, LiNO3Concentration is 0.1mol/L；Obtain product respectively with 1% dilute
HNO3Clean with deionized water, at 60 DEG C, be dried 24h.
2. one kind with titanium dioxide for titanium source synthesis Li adulterate PbTiO3The method of nano-particle, its
It is characterised by, comprises the steps:
1) 6.7g KOH is dissolved in 20ml deionized water is configured to the KOH aqueous solution of 6M, limit
Stirring limit is slowly added 6mmolTi0 inward2, stir 0.5h；
2) to step 1) gained solution is initially charged 6mmol Pb (NO3)2, add LiNO3With
Deionized water, obtains precursor pulp after stirring, move into the reactor of 50mL, airtight,
It is placed in 200 DEG C of insulations 12h, Hydrothermal Synthesis Li+Adulterated with Ca and Ti ore structure PbTiO3Nano-particle；
In described precursor pulp, LiNO3Concentration is 0.2mol/L；Obtain product respectively with 1% dilute
HNO3Clean with deionized water, at 60 DEG C, be dried 24h.
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| CN107651957B (en) * | 2017-10-12 | 2019-12-27 | 桂林理工大学 | Preparation of perovskite structure Pb1-xSnxTiO3Method for producing ceramic powder |
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